Compounds of the diazine series



Patented Sept. 27, 1932 UNITED STATES VJERNER SCHULEMANN, OF VOHWINKEL,

NEAR ELBERFELD, FRITZ MIETZSCH, OF

ELBERFELD, GERMANY, AND AUGUST WINGLER, OF WESTFIELD, NEW JERSEY,ASSIGNORS T WINTHROP CHEMICAL COMPANY, INC., OF NEW YORK, N. Y., A COR-PORATION OF NEW YORK COMPOUNDS 0! THE DIAZINE SERIES No Drawing.Application filed November 15, 1929, Serial No. 407,557, and in GermanySeptember 11, 1924.

The present invention relates to new compounds of the azine series, moreparticularly it relates to azines, being at least once substituted inthe benzene nuclei by a substituent of the general formula: I

N-R1-N Ra wherein m stands for hydrogen, or, for example, an alkylgroup, an aminoalkyl group, or substituted aminoalkyl group, such as amono alkylaminoalkyl group or dialkylaminoalkyl group, R stands for analkylene residue, in which the hydrogen atoms may be replaced bymonovalent substitutents, for example, by the hydroxy group, R and Rstand for alkyl groups which may be substituted, for example, by anamino group, and wherein the azine nucleus may be further substituted,for example, by alkyl, alkoxy, phenyl, halogen and the like.

The manufacture of our new compounds can be effected in several ways;for instance an amino derivative of an azine may be caused to be actedupon by an a-minoalkyl halide havin g the general formula:

wherein 7 represents a halogen atom, R an 3 alkylene residue thehydrogen atoms of which may be replaced by a monovalent substituent,such as the hydroxy group, R and R stand for hydrogen or alkyl groupswhich may be substituted, for example, by amino groups.

Instead of the aminoalkyl halide one may alkylamino derivatives "andsubsequently transforming the latter into the corresponding azinecompounds according to known methods. We are aware of the fact thatseveral other methods for preparing our new compounds are obvious which,however, we do not mention specifically. V

The new azine derivatives are generally yellow to violet products of alow melting point, generally sparingly soluble in water, soluble inorganic solvents; they yield, with inorganic acids, water-soluble Violetcolored salts, and are pharmaceutically valuable products. 7

The following examples illustrate our invention, without restricting itthereto:

Ewample 1 N- (methyl-diethylaminoethyl) -aminobenzone is prepared asfollows: 100 parts by weight. of monomethylaniline are heated underreflux for 24 hours with 135 parts by weight ofdiethylaminoethylchloride in a solution of 250 parts by weight of drybenzene. The hydrochloride of N- (methyl-diethylamino-ethyl)-aminobenzene thus produced is filtered off, washed with some benzeneand dissolved in water; the free base is separated with potassiumcarbonate. For the purpose of eliminating any quaternary ammoniumcompound, which may likewise have been salted out, the free base isdissolved in some benzene. After drying with potassium carbonate itdistils as a colorless liquid at 124126 C. (under 5 mm. pressure) afterthe separation of a slight preliminary fraction. Preparation ofthe azinecompound 20.6 grams of N- (methyl-diethylaminoethyl) -aminobenzene aredissolved in 20 cc. of concentrated hydrochloric acid with the additionof water and while cooling. Thereupon ice is added st-itution isobtainedby oxidationof the'leuoocompound with ferric chloride in thecold and salting out with a common salt solution; 1t

can be purified by redissolvingand again salting out. I

Example 2 t CH .4

OH2-CHi-N(C H5)2 1 5O gramsof4 nitro 2rtoluidine are'qui'clo l'y'heat'edin 150' grams of xylene with 150 grams of diethylaminoethylchloride inan oil batlrtoabout 140 C. and kept at this-temperature, for severalhours while stirring. Tothe cooled mixture water and ether areadded-andithus-an aqueous solution of the-hyd'rcchlor-i'c acid salt of1-methyl-2diethylaminoethylaminol nitrobenzene is obtained, while somestarting material, eventually present, is-=dissol ved in the etherxylene layer. The new base-is setfree by the addition of potassiumcarbonate; it is extracted with ether, dried, the ether isdistilled offand the new base is obtained as a thinly liquid bloody red oil-v havinga boiling point of 176 C. under a. pressure of L5 mm:

50 grams of iron borings are corroded with diluted aqueous-aceticacid,while boiling, and 50 grams of-theabove'new base, dissolved in thecalculated amount of normal hydrochlonic acidgare slowly introduced. Thered soluti'on' is'quickly decolorized'. When thereduction is complete,the solution is filtered, rendered alkaline,.and the reduction productis extracted with ether; The 1-methyl'-2-diethylaminoethylamino- 4aminobenz-ene' obtained is' a colorless'oilihaving a boiling'point of163 C. under a pressure" of 1 mm.

Theformation of the dyestu'flfof the-above formula is effected asdescribed in Example 1, bysubstituting 12.2g'ramsof'2-4-diaminotolueneby=22i1 grams of the new base. Thedyestuflissimil'ar to that described in Examplel'a This application isacontinuation in part of our application Ser. No. 52,228, filed August24, 1925, (U. S. Patent No. 1,766,403).

We claim: 1. As new products, the azine compounds of the probablegeneral formula:

being inv the form. of its mineral. acid. salts a bronze colored:powder, easily soluble in water with a. violet coloration.

3'. Asnewproducts, the azine compounds of! the probable generalformula:v

w-hereinX stands-for hydrogen or theradical I GH GH- .N-(C H saidcompounds being in the form ofv their mineral acidisaltssoluble inwater.

4. As a new product, the. azine compound of the formula:

. I O Nr N H3 Being in the form of' its mineral acid salts easilysoluble, in water.

In testimony whereof, we hereunto set our hands and affix our seals.

WERNER SCHULEMANN. [1,. s.] FRITZ MIETZSOH. [1 s.] AUGUST WINGLER. [L.s.]

